Acrylyl derivatives of fluorinated amides

ABSTRACT

WHEREIN X AND Y ARE INTEGERS FROM 2 TO 6 AND 1 TO 4, RESPECTIVELY; WHEREIN RF IS A PERFLUOROALKYL OR A FLUORINATED ISOALKOXYALKYL RADICAL; Z IS H, ALKYL, HYDROXYALKY, A FLUORINATED ACYL RADICAL RFCO- WHEREIN RF IS AS DESCRIBED ABOVE, OR AN ACRYLYL RADICAL; Z&#39;&#39; IS H, ALKYL, HYDROXYALKY, A FLUORINATED ACYL RADICAL RFCO- WHEREIN RF IS AS DESCRIBED ABOVE, AN ACRYLYL RADICAL OR A RADICAL HAVING THE FORMULA -CXH2XNHZ WHEREIN Z IS AS DESCRIBED ABOVE, THERE BEING AT LEAST ONE FLUORINATED ACYL RADICAL RFCO- AND AT LEAST ONE ACRYLYL RADICAL IN THE MOLECULE REPRESENTED BY Z AND/OR Z&#39;&#39;.   RF-CO-NH-(CXH2X-N(-Z&#39;&#39;))Y-CXH2X-NH-Z   ACRYLYL DERIVATIVES OF FLUORINATED AMIDES USEFUL AS OILAND WATER-REPELLENCY AGENTS HAVE THE STRUCTURAL FORMULA

3,576,018 ACRYLYL DERIVATIVES OF FLUORINATED AMIDES Richard F. Sweeney,Randolph Township, Morris County, and Alson K. Price, Morris Township,Morris County, N.J., assignors to Allied Chemical Corporation, New York,N.Y. No Drawing. Filed Aug. 1, 1968, Ser. No. 749,310 Int. Cl. C09f 7/00US. Cl. 260-4045 13 Claims ABSTRACT OF THE DISCLOSURE Acrylylderivatives of fluorinated amides useful as oiland water-repellencyagents have the structural formula wherein x and y are integers from 2to 6 and 1 to 4, respectively; wherein R is a perfluoroalkyl or afluorinated isoalkoxyalkyl radical; Z is H, alkyl, hydroxyalky, afluorinated acyl radical R CO wherein R is as described above, or anacrylyl radical; Z is H, alkyl, hydroxyalky, a fluorinated acyl radicalR;CO wherein R is as described above, an acrylyl radical or a radicalhaving the formula C H NHZ wherein Z is as described above, there beingat least one fluorinated acyl radical R CO- and at least one acrylylradical in the molecule represented by Z and/ or Z.

BACKGROUND OF THE INVENTION This invention is directed to a new class offluorocarbon derivatives and to their application to fibrous materialssuch as textiles and paper to produce oiland water-repellent products.More particularly, this invention relates to reaction products offluorinated polyamide compounds with acid halides of tat-unsaturatedcarboxylic acids, to treatment of textile, paper and other fibrousmaterials therewith to render the same oleophobic and hydrophobic, andto textile, paper and other fibrous products treated therewith so as tohave been rendered oiland water-repellent.

It is known to employ certain fluorochemicals in the treatment oftextile, paper and other fibrous products to impart thereto oilandwater-repellency properties. In general, these fluorochemicals arecomposed of a fluorinated alkyl chain aflixed to an active functionalgroup. The oleophobic and hydrophobic properties of the fluoro chemicalsare attributed, at least in part, to the inherent low surface energy ofthe fluorinated surface provided by the fluorinated alkyl chain. Theportion of the molecule to which the fluorinated alkyl chain is affixedprovides the physical and chemical bond between the fluorinated alkylchain and the substrate surface. This bond not only influences thedegree of orientation and packing of the fluorinated groups of thefluorinated alkyl chain, and hence, the oiland water-repellencyproperties of the fluorochemical, but in particular, determines thedurability of the oleophobic and hydrophobic properties obtained.

There is always a need for new oiland water-repellency agents,particularly for those which are not only capable of obtaining highlevels of oiland water-repellency, but are also capable of maintainingoleophobic and hydrophobic properties of substrate surfaces treatedtherewith after their repeated exposure to laundering.

Accordingly, one object of the present invention is the provision ofnovel fluorocarbon derivatives.

nited States Patent for Another object is to provide oilandwater-repellent compositions of novel fluorocarbon derivatives suitablefor treating fibrous materals, such as paper and textiles, to impartthereto oleophobic and hydrophobic properties.

A still further object is to provide methods for the treatment oftextiles, paper and other fibrous products, employing said fluorocarbonderivatives.

A further object is to provide textile and paper materials treated withthe fluorocarbon derivatives of the present invention.

These and other objects will be apparent from the following description.

DESCRIPTION OF THE INVENTION In accordance with the present invention,reaction products of fluorinated polyamide compounds with acid halidesof certain tat-unsaturated carboxylic acids have been found to impart totextiles, paper and other fibrous products durable oilandwater-repellency properties.

The compounds proposed for use as oiland waterrepellency agents conformto the general formula:

wherein (1) Rf is a radical selected from the group consisting (a)perfluoroalkyl having from 3 to 17 carbon atoms, and (b) a radicalhaving the formula wherein (i) R and R are fluorine or are fluoroalkylgroups, or when taken together, are fluoroalkylene groups forming acycloaliphatic structure, which R and R groups may each have from 1 to 9carbon atoms, provided that not more than three of the R and R groupsmay be fluoroalkyl groups, (ii) m and n are each integers of from 0 to20, with the proviso that the sum of m and n is from 0 to 20, andprovided further that when r is 0, m is at least 1, (iii) X is selectedfrom the group consisting of hydrogen and fluorine, with the provisothat when n is greater than 0, then X is always hydrogen, (iv) p is 0 to1, (v) r is O or 1, with the proviso that when the sum of m, n and p isgreater than 0, then r is always 0, (2) x is an integer from 2 to 6, (3)y is an integer from 1 to 4, (4) Z is a member selected from the groupconsisting (a) hydrogen, (b) alkyl having from 1 to 6 carbon atoms, (c)a radical having the formula ROH wherein R is a divalent alkylenebridging group containing from 1 to 6 carbon atoms,

(e) an tit-unsaturated acyl radical having the formula in which R, and Rand R are independently selected horn the group consisting of hydrogenand alkyl having from 1 to 6 carbon atoms, and (5) Z, which may be thesame or different in different Z! (o,H2,N)

groups, is a member selected from the group consisting of (a) hydrogen,(b) alkyl having from 1 to 6 carbon atoms, (c) a radical having theformula ROH wherein R is a divalent alkylene bridging group containingfrom 1 to 6 carbon atoms, (d) a fluorinated acyl radical having theformula i C-Rt wherein R; has the afore-stated meaning,

(e) an tat-unsaturated acyl radical having the formula 0 R /R b-iho inwhich R R and R have the afore-stated meanings, and (f) a radical havingthe formula C,H2;NZ

wherein x and Z have the afore-stated meanings, with the proviso that atleast one of Z or Z is a fluorinated acyl radical or one of Z is aradical having the formula wherein Z is a fluorinated acyl radical, andat least one of Z or Z is an car-unsaturated acyl radical or one of Z isa radical having the formula H C =H2XII\IZ wherein is an tit-unsaturatedacyl radical, said fluorinated acyl radical and (at-unsaturated acylradical having the afore-stated formulas.

The novel fluorocarbon derivatives of the present invention are preparedby reacting a fluorinated polyamide starting material as hereinbelowdefined with an u-unsaturated acyl halide reactant at temperaturesbetween about 0 C. to about 160 C., preferably in the presence of aninert organic solvent.

The a-unsaturated acyl halide reactants employed in the preparation ofthe novel fluorocarbon derivatives of the present invention, as a class,are known compounds which are represented by the formula 'wherein R, Rand R are independently selected from the group consisting of H andalkyl having from 1 to 6 carbon atoms, and wherein A is a halogenselected from the group consisting of F, Cl, Br and I. Acrylyl chloride,methacrylyl fluoride, 2,3,3-trihexylacrylyl fluoride,3,3-dihexylmethacrylyl chloride, 3butyl-Bethyl-B-propylacrylyl iodide,3-propyl-3ethyl-methacrylyl fluoride, 3-hexyl- 3-ethylacrylyl chloride,2,3-dihexylacrylyl bromide, 3- amylacrylyl fluoride, 3,3-diethylacrylylfluoride, 3-ethyl-2- hexylacrylyl bromide, 3-ethylmethacrylyl chlorideand 3,3-diethylmethacrylyl chloride are illustrative of a-unsaturatedacyl halide reactants suitable for making novel fluorocarbon compoundsof the present invention.

The fluorinated polyamide reactant suitable for reaction with the abovea-unsaturated acyl halide reactants is characterized by the structuralformula:

Y! R li l 1'- C xII2;1 I) G xHixl lY (II) wherein R x and y have theabove-stated meanings; Y is a member selected from the group consistingof hydrogen, alkyl having from 1 to 6 carbon atoms, a radical having theformula ROH wherein R 'has the abovestated meaning and a fluorinatedacyl radical having the formula wherein R, has the above-stated meaning;and Y, which may be the same or different in different 'IYI (CXH2XN)-groups, is a member selected from the group consisting of hydrogen,alkyl having from 1 to 6 carbon atoms, a radical having the formula ROHwherein R has the above-stated meaning, a fluorinated acyl radicalhaving the formula wherein R; has the above-stated meaning and a radicalhaving the formula o,H2,-N-Y wherein x and Y have the above-statedmeanings, with the proviso that at least one of Y or Y is a fluorinatedacyl radical or one of Y is a radical having the formula C,H2;NY

in which x is as stated above and Y is a fluorinated acyl radical, saidfluorinated acyl radical having the aforestated formula, and at leastone of Y or Y is hydrogen.

The fluorinated polyamide reactant of Formula II, above IS prepared byreaction of a fluorinated carboxylic acid having the formula R COOHwherein R, has the afore-stated meaning, or a derivative thereof, suchas an ester, anhydride or acid halide thereof with a polyalkylenepolyamine compound corresponding to the general formu a NH: o xHarl n yCxHaNHQ wherein x and y have the afore-stated meanings; wherein Q isselected from the group consisting of hydrogen, alkyl having from 1 to 6carbon atoms, and a radical having the formula ROH wherein R has theafore-stated meanmg; and wherein Q is selected from the group consistingof hydrogen, alkyl having from 1 to 6 carbon atoms, a radical having theformula ROH wherein R has the afore-stated meaning, or an aminoalkylradical having the formula C H NHQ wherein x and Q have the afore-statedmeanings; there being at least two hydrogen atoms in the moleculerepresented by Q and/or Q.

The polyalkylene polyamine reactants of Formula III, above, employed inthe preparation of the fluorinated polyamide compounds of Formula II,above, as a class,

are known compounds. These reactants may be straightchain orbranched-chain compounds and may be used in the form of a singlecompound, as a mixture of isomers or as a mixture of polyaminescontaining from 3 to 6 nitrogen atoms in the molecule. Specific examplesof polyalkylene polyamines employable herein include diethylenetriamine, di r1 propylene triamine, di-butylene triamine, di-n-hexylenetriamine, triethylene tetramine, tri-i-propylene tetramine, tri nhexylene tetramine, 4- (2 aminoethyl) 1,4,7 triazaheptane, tetraethylenepentamine, tetra n propylene pentamine, tetra-n-butylene pentamine, 4 (2aminoethyl) 1,4,7,l tetraazadecane, tetra n hexylene pentamine,pentaethylene hexamine, 1 (hydroxyethyl) 1,4,7 triazaheptane, 1- methyl8 (6 heydroxyhexyl) l,4,8,12 tetraazadodecane,1-(6-hydroxyhexyl)l1,16-dimethyl 1,11,16,21- tetraazaheneicosane, 1,7bis(2 hydroxyethyl) 1,4,7, 10 tetraazadecane, 4 methyl 1,4,7,10tetraazadecane, and l-methyl 1,5,9 triazanonane. These polyalkylenepolyamines can be prepared by standard methods known to those skilled inthe art. Preferred polyalkylene polyamines are diethylene triamine,dipropylene triamine,

triethylene tetramine and tetraethylene pentamine since these are themore readily commercially available compounds.

Fluorinated carboxylic acid reactants, above described, wherein R isperfluoroalkyl, suitable for reaction with the above polyalkylenepolyamine reactants are saturated straight-chain or branched-chainmonocarboxylic acids or stated derivatives thereof containing from 4 to18 carbon atoms in the acid portion of the molecule. Discrete molecularspecies of the perfluorocarboxylic acid reactants may be used ormixtures of these reactants in various proportions having the indicatedcarbon chain length may be employed. Illustrative perfiuorocarboxylicacid reactants include perfluorobutyric, perfiuorocaproic,perfluorocaprylic, perfluorolauric, perfluoromyristic,perfluoropalmitic, and perfluorostearic acids, as well as variousisomeric forms thereof.

Perfluorocarboxylic acid reactants herein contemplated containing up toabout ten carbon atoms are readily prepared by the electrochemicalfluoroination of alkanoic acids in anhydrous hydrogen fluoride withsubsequent hydrolysis of the resulting fluorinated acid fluorides, asdisclosed in US. Pat. 2,567,011, issued Sept. 4, 1951. Longer chainperfluorocarboxylic acid reactants, i.e. those containing from about 11to 18 carbon atoms, may be obtained by reaction of perfluoroalkyliodides with oleum containing about 15% to 45% sulfur trioxide atelevated temperatures followed by hydrolysis of the resultingperfluorocarboxylic acid fluoride, as disclosed in French Pat. 1,343,601of Oct. 14, 1963.

Fluorinated carboxylic acid reactants, above described, wherein R, is aradical having the formula wherein R R X, r, n, m and p have theafore-stated meanings may be prepared by various hereinafter describedmethods.

Fluorinated carboxylic acids of the formula R COOH wherein R; has theFormula IV, above, wherein m is at least 1 and the sum of n and p is atleast 1, can be prepared from telomers having the general formulawherein R and R have the afore-stated meanings, wherein s and t are eachintegers from 0 to 20, the sum of s and I being at least 1, and whereinE is a halogen selected from the group consisting of Br and I. Telomersof that type and their preparation are described in commonly assignedcopending application of Anello et al. entitled, Telomers and Processfor the Preparation Thereof, Ser. No. 633,359, filed Apr. 25, 1967 nowU.S. Pat. 3,514,487, the pertinent subject matter of which is herebyincorporated by reference. By way of general description, these telomersare prepared by radical addition reactions of polyfluoroisoalkoxyalkylhalide telogens of the formula wherein R R and E have the afore-statedmeanings, with telomerizable unsaturated compounds. The telomerizationreaction may be initiated by heat or by means of a free radicalinitiating catalyst. The polyfluoroisoalkoxyalkyl halide telogenstarting materials may be prepared by reacting a correspondinghalogenated ketone with an ionizable flouride salt, e.g. C F, to form afluorinated organic salt and then reacting the organic salt with ahalogen other than fluorine and an olefin. Preparation of the telogenstarting materials is described in detail in copending applications ofLitt et al., Fluorinated Ethers, U.S. Ser. Nos. 492,276 and 513,574,filed Oct. 1, 1965, and Dec. 13, 1965, respectively now US. Pats.3,453,333 and 3,470,256 respectively, the pertinent subject matter ofwhich applications is hereby incorporated by reference.

Fluorinated carboxylic acids of the formula R COO'H wherein R has theFormula IV, above, wherein r, n and p are all 0 and wherein m is atleast 2 may be prepared by reacting the corresponding telomerrepresented by general Formula V, above, wherein t is 0 with ICN or (CN)to form the nitrile, followed by hydrolysis of the nitrile in knownmanner to form the free acid. The reaction between the telomer and theICN or (CN) to form the nitrile is carried out under superatmosphericpressure above about 20 to 200 atmospheres or more at temperatures inexcess of about 300 C., preferably using an excess of the ICN or (CN)reactant. Hydrolysis of the nitrile to form the free acid can beeffected by treatment with aqueous mineral acid, such as hydrochloric,phosphoric, or sulfuric acid, at temperatures between about 60 and about125 C.

Fluorinated carboxylic acids of the formula R COOI-I wherein R has theFormula IV, above, wherein m is at least 1, p and r are both 0 and n isgreater than 0 may be prepared by reacting the corresponding telomerrepresented by Formula V, above, wherein t is greater than 0 with analkali metal cyanide to form the nitrile, followed by hydrolysis of thenitrile to form the free acid, as described above. The reaction betweenthe telomer and the alkali metal cyanide is preferably carried out inaqueous alcoholic solution at temperatures between about 60 and about C.

Fluorinated carboxylic acids of the formula R COOH wherein R has theFormula IV, above, wherein m is at least 1, r is O, p is l and X ishydrogen can be prepared by reacting the corresponding telomerrepresented by general Formula V, above, wherein t is at least 1 with S0to form the corresponding pyrosulfate, or with oleum to form thecorresponding hydrosulfate, hydrolysis of the pyrosulfate or thehydrosulfate with aqueous acid to form the corresponding alcohol,followed by oxidation of the alcohol with dichromate, permanganate orstrong nitric acid to form the free acid.

Fluorinated carboxylic acids of the formula R COOH wherein R, has theFormula IV, above, where m is at least 1, r and n are both 0, p is 1 andX is fluorine can be prepared by reacting a corresponding telomerrepresented by Formula V, above, wherein t is with $0 to formcorresponding acid halides and halopyrosulfates, and hydrolyzing theacid halides and halopyrosulfates by refluxing with water to obtain thecorresponding free acids. Fluorinated carboxylic acids of the formula RCOOH wherein R: has the Formula IV, above, wherein r is 1 and m, n and pare all 0 can be prepared by the same method frompolyfluoroisoalkoxyalkyl halide compounds of Formula VI, above.

Fluorinated carboxylic acids of the formula R COOH wherein R; has theFormula IV, above, wherein mis 1 and r, n and p are all 0 can beprepared from polyfluoroisoalkoxyalkyl halide compounds of Formula VI,above, by reacting them with a Grignard reagent to form a magnesiumhalide adduct, reacting this adduct with CO to form a magnesium halidesalt, and then acidifying the salt to obtain the desired acid. Thereactions involving the Grignard reagent and the carbon dioxide proceedvery rapidly and can be conducted at tempera tures considerably below 0C. Preparation of these acids is described in detail in commonlyassigned co-pending application of Litt et al., Fluorinated Ethers, U.S.Ser. No. 492,276, filed Oct. 1, 1965, now U.S. Pat. 3,453,- 333,referred to above.

The esters and acid halides of the above-described acids may be preparedfrom the acids by conventional procedures.

While the telomers of Formula V, above, and the fluorinated carboxylicacid reactants derived therefrom, may be prepared as discrete compounds,they are generally obtained as mixtures of compounds of varying chainlength. It is to be understood that both, the individual discretefluorinated carboxylic acid reactants as well as their mixtures ofcompounds of varying chain length are suitable for the preparation ofthe fluorinated polyamide compounds employed in the preparation of thecompounds of the present invention.

Preparation of the above-described acids wherein R, has the Formula IV,above, is described in more detail in commonly assigned copendingapplications of Anello et al., U.S. Ser. Nos. 721,115 and 721,117, bothfiled Apr. 12, 1968, respectively entitled Fluorocarbon Acids andDerivatives and Fluorocarbon Compounds, the pertinent subject matter ofwhich application is hereby incorporated by reference.

The fluorinated polyamide reactants of Formula II, above, may beprepared by simply mixing the fluorinated carboxylic acid reactant withthe polyalkylene polyamine Starting material of Formula III, above.These reactants may be charged in a molar proportion of 1 mol ofpolyalkylene polyamine to about 1 to 7 mols of fluorinated carboxylicacid reactant. If desired, the reaction may be carried out in thepresence of a suitable inert organic solvent. Suitable reactiontemperatures range between about 0 C. to about 200 C. Upon conclusion ofthe reaction, the desired fluorinated polyamide compound may berecovered from the reaction mixture by methods known to those skilled inthe art.

The reaction product, obtained as a result of the reaction of thefluorinated carboxylic acid reactant and the polyalkylene polyaminereactant above described, may comprise a single compound conforming tothe above stated structural Formula II, a mixture of isomers thereof ora reaction mass composed of amide products containing two or more amidefunctions depending upon the polyalkylene polyamine reactant employed,the reactivity of the fluorinated carboxylic acid reactant present, thesolubility of the amide product obtained during the reaction in thereaction mixture and the molar proportions of fluorinated carboxylicacid reactant employed. The resulting fluorinated polyamide productwhether it comprises a single compound, a mixture of isomers thereof ora mass composed of amide products containing tWo or more amidefunctions, is suitable without further purification for reaction withthe wunsaturated acyl halide reactant, above described, to form thefluorocarbon derivatives of the present invention. However, if desired,the fluorinated polyamide may be further purified prior to reaction withthe tar-unsaturated acyl halide reactant, as by distillation orrecrystallization using any commonly employed inert organic solvent suchas acetonitrile or chloroform.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel fluorocarbonderivatives of this invention are prepared by reacting the a-unsaturatedacyl halide reactant with the fluorinated polyamide starting material,above described. These reactants may be charged in a mol proportion of 1mol of fluorinated polyamide to about 1 to 10, preferably about 2 to 4,mols of tat-unsaturated acyl halide reactant. Reaction temperature andtime are dependent upon the particular fluorinated polyamide andzit-unsaturated acyl halide reactants involved. The temperature rangesfrom about 0 C. to about 160 C., preferably about 10 C. to about C. Thereaction is quite rapid even at about room temperature. Reaction timesgenerally range between about 10 minutes and about 4 hours. If desired,the reaction may be conducted in the presence of an inert organicsolvent and, when present, the maximum temperature employable is limitedonly by the reflux temperature of the reaction mixture. Although thereaction may be carried out under superatmospheric pressure, it ispreferred to conduct the reaction at atmospheric pressure.

The reaction of the fluorinated polyamide starting material with thetat-unsaturated acyl halide reactant yields as by-product the halidesalt of the polyamide starting material, as illustrated by the equationbelow which shows the reaction of 1,7-bis(perfluorooctanoyl)-1,4,7-triazaheptane with acrylyl chloride:

Upon completion of the reaction the desired product can be extractedfrom the reaction mixture using a suitable solvent, such as ether,acetone, acetonitrile, and the like, and can be purified, as e.g. byfractional crystallization. In a preferred embodiment the reaction iscarried out in an acetone medium. Acetone dissolves the starting materials and the desired product, but not the by-product halide salt.Thus, recovery of the desired product is facilitated in that, uponcompletion of the reaction, the reaction, the by-product halide salt canbe simply removed by filtration of the reaction mixture. The halide saltby-product can be reconverted to the fluorinated polyamide startingmaterial in known manner by treatment with an appropriate ion exchangeresin or with an aqueous base, such as aqueous sodium hydroxide.

To prevent polymerization of the tat-unsaturated acyl halide reactantduring the reaction, it is preferred to conduct the reaction in thepresence of one of the Well known free radical inhibitors, such asu-pinene. The free radical inhibitor, if one is used, is employed inamount of between 0.01% to about 1.0% by weight, based on the totalWeight of the reaction mixture.

The reaction is preferably carried out in the presence of anacid-interceptor, such as sodium bicarbonate, to thereby increase theyield of the desired product and to reduce the amount of by-producthalide salt formed in the reaction.

Since the tit-unsaturated acyl halide reactant is decomposed by Water,the reaction is preferably carried out under exclusion of water usinganhydrous reagents.

The alkylene linkage (C H in the novel compounds of the presentinvention may be a straight-chain or branched-chain group, preferablycontaining from 2 to 4 carbon atoms.

The R groups in the novel fluorocarbon derivatives of the presentinvention represented by Formula I, above, may be the same or different.When the R; group is a perfluoroalkyl group, it may be straight-chain orbranchedchain, preferably containing from 6 to 14 carbon atoms.

When the R; group is a fluorinated isoalkoxyalkyl group represented byFormula IV, above, then, in the moiety, R and R are preferably fluorineor perfluoroalkyl groups. When perfluoroalkyl groups, R, and Rpreferably contain 1-2 carbon atoms. When the R and R groups containhydrogen substitution, the atomic ratio of fluorine to hydrogen is atleast 1: 1.

In preferred embodiments integer m in the Rf radical of Formula IV,above, is at least 1, and the sum of m and n is preferably from 1 to 10.Specific examples of preferred embodiments of the preferred moiety ofthe R radical of the compounds of the present invention include thefollowing:

(VII) wherein R R R R and y have the aforestated mean ings and x is aninteger from 2 to 4 constitute preferred embodiments of the presentinvention, those wherein R is selected from the group consisting of Hand methyl, and wherein R and R are independently selected from thegroup consisting of H and alkyl having from 1 to 2 carbon atoms beingmore preferred yet. Acrylyl and methacrylyl 10 radicals are specificexamples of preferred tit-unsaturated acyl radicals.

A specific class of preferred embodiments of the present invention arecompounds according to Formula VII, above, wherein the R; radical hasthe formula wherein m is an integer from 1 to 10, n is an integer from 0to 10, with the proviso that the sum of m and n is from 1 to 10, andwherein X and p have the aforestated meanings.

The following examples relate to the preparation of representativecompounds of the present invention but are not intended to be limitingon the scope thereof.

EXAMPLE 1 Sodium bicarbonate (17.8 g., 0.21 mol) and ten drops ofa-pinene are added to a stirred solution of1,7-bis(perfluorooctanoyl)-l,4,7-triazaheptane (53 g., 0.06 mol) in 500ml. of acetone at 10 C. To this mixture is added under constant stirringa total 9.0 g. (0.1 mol) of acrylyl chloride, and stirring at 1015 C. iscontinued for three hours. After that time the reaction mixture isfiltered to remove insoluble material, and the clear filtrate isevaporated to dryness to yield about 30 g. of crude product. The crudeproduct is twice recrystallized from acetonitrile to yield about 20 g.of the colorless solid product, 1,7-bis-(perfluorooctanoyl)-4-acrylyl-2,4,7 triazaheptane, having the formula Aportion of that product is subjected to further recrystallization fromacetonitrile to yield an analytical sample (M.P. 115116 0.).

Analysis.Calcd. for C H O N F (percent): C, 29.1; H, 1.39; N, 4.42; F,60.0. Found (percent): C, 29.4; H, 1.14; N, 4.78; F, 59.26.

Assigned structure is confirmed by infrared spectrographic analysis.

The 1,7-bis (perfluorooctanoyl) -1,4,7-triazaheptane reactant isprepared in the following manner:

A solution of 49 grams (0.475 mol) of diethylene triamine in 60 ml. ofdiethyl ether is placed in a reaction vessel equipped with a droppingfunnel, condenser, magnetic stirrer and a calcium chloride drying tube.After chilling the vessel in an ice water bath for a period of about 20minutes, 34.2 grams (0.079 mol) of n-perfluorooctanoyl chloride is addedwith stirring to the contents of the vessel during a 30 minute period.After addition of the n-perfluorooctanoyl chloride reactant is complete,the ice water bath is removed and the stirring is continued at roomtemperature for a period of 20 minutes. Thereafter ml. of an 8% aqueoussodium hydroxide solution is added to the reaction mixture and thestirring is continued for an additional 15 minutes. The resultinggelatinous precipitate is filtered at reduced pressure and Washed withwater. After air drying the precipitate, a yield of about 30 grams of1,7-di-n-perfluoro0ctanoyl-1,4,7-triazaheptane, a white solid (meltingpoint 9497 C.), having the following structural formula is obtained:

EXAMPLE 2 Following the procedure of Example 1 there is reacted1,9-di-n-perfluorooctanoyl-1,5,9-triazaheptane with methacrylyl fluorideto obtain as product the compound The1,9-di-n-perfluorooctanoyl-1,5,9-triazaheptane reactant is prepared inthe following manner:

To a solution of 20 grams (0.0467 mol) of methyl-m perfluorooctanoate in25 ml. of diethyl ether, there is added 3.07 grams (0.0235 mol) ofdi-n-propylene triamine. The resulting solution is heated under refluxtemperature for a period of 24 hours. After removal of the solvent underreduced pressure, 16.6 grams of a light yellow oil which solidifies inabout 30 minutes to give a white sticky solid is obtained. The whitesticky solid is recrystallized from acetonitrile to yield1,9-di-n-perfluorooctanoyl-1,5,9- triazanonane (a white powder meltingat 84-85 C.) having the following structural formula:

EXAMPLE 3 Following the procedure set forth in Example 1 there isreacted the amide with methacrylyl chloride to obtain as product thecompound The amide reactant is prepared in the following manner: To asolution of 24.7 g. (0.05 mol) of in 25 ml. of diethyl ether there isadded 3.07 g. (0.0235 mol) of di-n-propylene triamine. The resultingsolution is heated under reflux for a period of 24 hours. After removalof the solvent under reduced pressure there is obtained the crudeproduct (CF CFO (CF CONHCH CH CH NH which can be purified byrecrystallization from acetonitrile.

EXAMPLE 4 Following the procedure set forth in Example 1 there isreacted l,lO-di-n-perfluorooctanoyl-1,4,7,lO-tetraazadecane with acrylylbromide to obtain as product the compound The 1,IO-di-n-perfluorooctanoyl-1,4,7, lO-tetraflzadecane reactant is preparedin the following manner:

To a solution of 20 grams (0.0467 mol) of methyl-nperfluorooctanoate in25 ml. of diethyl ether, there is added 3.4 grams (0.0233 mol) oftriethylene tetrarnine. The resulting solution is heated under refluxtemperature for a period of 24 hours. After removal of the solvent underreduced pressure, 20 grams of a white solid is obtained which issubsequently recrystallized from acetonitrile. The product of thisreaction is 1,10-di-n-perfiuorooctanoyl-1,4,7-tetraazadecane, a whitepowder (melting point 89-92 C.) having the following structural formula:

OH H H HO EXAMPLE 5 To a solution of 16 grams (0.037 mol) of methylperfiuorooctanoate in 20 of diethyl ether there is added 3.5 grams(0.018 mol) of tetraethylenepentamine. The resulting solution is heatedto reflux temperature for a period of 3 hours. After removal of thediethyl ether solvent under reduced pressure there remains a viscousyellow oil which does not solidify on standing. This oil is dissolved in250 ml. of acetone, 16.0 g. (0.19 mol) of sodium bicarbonate and 5 dropsof a-pinene are added, the solution is stirred, and 9.4 g. (0.09 mol) ofmethacrylyl In manner analogous to that described in the above examples,other compounds illustrative of the present invention may be prepared asfollows:

iodide.

CF3 Fa O 0E3 CF F- -cFlor(orm-(i-Nnczmtvclmib-ii-tormcForge-F CFs C41193 s by reaction of 1,7-di-[(4,6-di-trifluoromethyl)perfluoroheptanoyl]-l,4,7-triazaheptane with 2-ethyl-3-butyl-3- byreaction of 1,7-di-n-perfluorotetradecanoyl-l,4,7-triaza heptane with3-ethyl-3-hexylacrylyl bromide.

by reaction of 1,7-di-n-perfluorohexadecanoyl-1,4,7-triazaheptane with2,3-dihexylacrylyl chloride.

ll 0 CH3 GsHis by reaction ofl,lO-di-n-perfluorononanoyl-l,4,7,10-tetraazadecane with3-hexylmethacrylyl fluoride.

by reaction of 1,l0-di-[(3,5,7-tris-trifluoromethyl)perfiuorononanoyl]-1,4,7,l0-tetraazadecane with 3 -butyl acrylylchloride.

15 by reaction of 1,10 n-diperfluorooctanoyl-4-(2-aminoethyl)-l,4,7,10-tetraazadecane with 3-amylmethacrylyl chloride.

by reaction of1,l--di-n-perfluorooctanoyl-4-(Z-n-perfluorooctanamidoethyl)-1,4,7,l0-tetraazadecanewith acrylyl chloride.

by reaction of1,10-n-diperfluorooctanoyl-4-(2-aminoethyl)-l,4,7,lO-tetraazadecane withacrylyl chloride.

The oiland water-repellent compounds of the invention are useful intreating paper as Well as textiles (fabrics and fibers) comprised ofnatural or synthetic fibers including cotton, nylon, wool, polyethyleneterephthalate and polyacrylonitrile. The fluorocarbon derivatives of theinvention are especially useful in the treatment of fabrics and fiberscomprised of cellulosic and certain cellulosic derivatives which containcellulosic hydroxyl groups such as cotton, linen, viscose, cupraammonium rayon, saponified cellulose acetate and salts of cellulosexanthate. The invention is also applicable to the treatment of blends ofnatural and/or synthetic fibers in cloth, for example, blends containingpolyethylene terephthalate, polyacrylonitrile, nylon, cotton and wool.If desired, auxiliary agents such as those imparting water repellency,crease resistance and softening properties may be applied in conjunctionwith the fluorocarbon chemicals of the invention. In addition, othermaterials such as the surfaces of wood, plastics, glass and metals maybe treated with solutions or suspensions containing the fluorocarbonderivatives of the invention to render the same oiland water-repellent.

The fluorocarbon derivatives of the present invention may be applied tothe article to be rendered oiland water-repellent by treating the samewith a solution of the repellent and evaporating the solvent. Ifdesired, the treated article may then be cured at an elevatedtemperature. The concentration of the fluorocarbon derivative on thetreated article generally may vary from about 0.5% to preferably 1.0% to4.0%, based on the weight of the article. Since the solvent used informulating the oiland Water-repellent composition functions essentiallyas a carrier for the fluorocarbon derivative, any organic liquid inertto the article to be treated and capable of dissolution of the requisiteamount of oiland Water-repellency agent may be employed. Acetone, methylethyl ketone, acetonitrile and dimethylformamide are illustrativesolvents which may be used in preparing the oiland water-repellentcompositions. Alternatively, aqueous emulsions of the oilandwater-repellent may be applied onto the articles to be treated byconventional aqueous application methods.

The solvent may be evaporated by air drying at room temperature. If itis desired to cure the treated articles the solvent may be evaporatedprior to curing or during curing of the oiland water-repellent chemicalonto the article. Preferably, the article treated with a solution of thefluorocarbon derivative is air dried prior to curing for a timesuflicient to evaporate essentially all of the solvent. Thereafter, thearticle having on its surface the oiland water-repellent chemical iscured or heat-set at a temperature of about 100 C. to 160 C. for a timeperiod varying inversely with the temperature, ranging from about 1second to 5 minutes.

When cellulosic materials are to be rendered oiland Water-repellent, thefluorocarbon derivatives of the present invention are preferably appliedthereto from an aqueous solution or an aqueous emulsion and in thepresence of a catalyst of the type commonly used as crosslinkingcatalyst for crosslinking resins with cellulosic materials. Thefluorocarbon derivatives of the present invention respond equally Wellto basic as well as acidic catalysts, thus, have the decided advantagethat their use is compatible with permanent press treatment, whichtreatment commonly employs acidic reactants. The cellulosic material ismoistened with an aqueous solution of the catalyst, air dried to removeresidual Water and then impregnated with an aqueous solution or emulsionof the fluorocarbon derivative of the invention for a time, normally 30seconds to about 30 minutes, sufficient to retain on the cellulosicmaterial about 1 to 10%, preferably 2 to 4% of the fluorocarbonderivative, based on the weight of the cellulosic material. The thuslyimpregnated cellulosic material is then heated at a temperature of C. toC. for a time period varying inversely with the temperature ranging fromabout 15 minutes to 30 seconds. After the reaction of the fluorocarbonderivative with the cellulosic material is complete, the chemicallymodified cellulosic material is Washed free of excess catalyst withwater and dried.

Various modifications of the above-described treatment may also beemployed without departing from the spirit of the invention. Forexample, the cellulosic material may be first impregnated with anaqueous solution or emulsion of the fluorocarbon derivative, thentreated with an aqueous solution of the catalyst, air dried and finallyheated to effect reaction of the fluorocarbon derivative With thecellulosic material. Another modification of the above-describedprocedure involves premixing the aqueous solution or emulsion of thefluorocarbon derivative together With the catalyst prior to impregnationof the cellulosic material. Chemical modification of the cellulosicmaterial under anhydrous conditions, as in the presence of solventscapable of penetrating cellulosic fibers such as benzene, chloroform,dioxane and acetone, constitutes still another variation of theafore-described procedures.

In general, suitable basic catalysts should have a dis associationconstant in water of at least 1.8)(10 at 25 C. Phosphates, carbonatesand hydroxides of alkali metals such as sodium phosphate, sodiumcarbonate, sodium hydroxide and potassium hydroxide; alkaline-earthmetal hydroxides including calcium hydroxide and magnesium hydroxide;and quaternary ammonium hydroxides such as tetraethyl ammonium hydroxideand benzyl trimethyl ammonium hydroxide are illustrative of preferredeffective basic catalysts. Suitable acid catalysts are the mineral acidsand strong organic acids, as well as the ammonium salts, amine salts andmetal salts of strong acids. The salts of strong acids are preferredacid catalysts, ammonium chloride, magnesium chloride, zinc nitrate andzinc chloride being specific examples of preferred acid catalysts. Thecatalyst concentration is normally dependent upon the strength of theacid or base catalyst selected, speed of reaction desired and the natureof the cellulosic material to be treated. In general, catalystconcentrations of about 1 to 20%, preferably 2 to 5%, based on theWeight of the solution are satisfactory.

Results of tests relating to the evaluation of a typical fluorocarbonderivative composition of the present invention as oilandwater-repellency agent on textiles are shown below.

The procedure employed in determining the oil-repellency ratings ontextiles is described, for example, on pages 323-4 of the April 1962edition of the Textile Research Journal. This procedure involves gentlyplacing on the treated fabric drops of mixtures of mineral TABLE IOll-repelleney Percent Percent rating mineral oil a n-heptane b 10 Noholdout to mineral oil Nujol Saybolt viscosity 360/390 at F. Specificgravity 0.880/0.900 at 60 F. Percent by volume at 20 C.

b IEEegtane B.P. 9899C. Percent by volume When typical oily stainingmaterials are dropped onto treated fabrics and subsequently blotted 01f,those fabrics with an oil-repellency rating of 50-70 will exhibit onlyfair resistance to staining; those fabrics with an oil-repellency ratingof 80-90 will have good resistance to staining; and those with anoil-repellency rating of 100 and up will give excellent resistance.

Wash fastness of the treated cloth was determined by subjecting thecloth to repeated launderings in hot wat r in a household automaticwashing machine using a heavy duty detergent, followed by drying in anautomatic drier. The material was ironed prior to testing.

The results obtained are set forth in Table II below:

(b) Same as in (a) above, except that prior to impregnation with theacetone solution of the fluorocarbon compound the test pieces weretotally immersed in a 5% aqueous magnesium chloride solution, were wrungout, and were then dried at 80 C. for 8 minutes.

(0) Same as in (a) above, except that prior to impregnation with theacetone solution of the fluorocarbon cornpound the test pieces weretotally immersed in a 5% aqueous sodium hydroxide solution, were wrungout, and were then dried at 80 C. for 8 minutes.

When water was placed on test pieces impregnated as shown above, thewater did not penetrate the fabric, but formed beads on the surfacethereof which could be removed as by shaking the fabric. Thus, thefabric so treated had oilas well as water-repellent properties.

The result of a test relating to the evaluation of a typicalfluorocarbon derivative of the present invention as oil-repellency agenton paper is shown below.

The procedure employed in deterimining the oil-repellency ratings onpaper is described, for example, in a Technical Bulletin issued by theMinnesota Mining and Manufacturing Company, entitled Paper Chemical FC-805-IV. Properties of Treated Paper-C. Oil Resistance- 2. ComparativeKit Test. This procedure involves gently placing on treated paper dropsof mixtures of castor oil, toluene and heptane in varying proportions.The drops are allowed to stand on the treated paper undisturbed for 15seconds. After the 15 second period the wetting and penetration of thepaper is visually observed. Failure is detected by pronounced darkeningcaused by penetration. The darkening of even a small fraction of thearea under the drop is considered failure. Referring to following TableIII, the number corresponding to the mixture containing the highestpercentage of heptane which does not penetrate or wet the paper is theKit Number of the paper and is considered to be the oil-repellencyrating of the treated paper.

TABLE II Oil repellency alter launderings Speci- Substrate men 0 l 2 3 45 6 Cotton print cloth a 150 120 80 60 80 60 Spun nylon cloth a 110 70Type 54 Dacron/cotton blend cloth-.." a 140 120. 110 110 100 100 Thetest specimens, pieces of 80 x 80 count white cot- TABLE III ton printcloth, spun 100% Nylon cloth, Type 54 Dacron (T.M.)/cotton blend poplinweight cloth, were treated oasto r oil, Tollllene, Heptane, with a 1.75percent solution of 1,7-bis (perfluorooctanoyl)- 65 ume Wlum"4-acrylyl-1,4,7-triazaheptane in acetone as follows: 200 0 o (a) Thetest specimens were impregnated by total un- 1: "j: 180 10 10 mersion inthe acetone solution of the fluorocarbon com- E3 g3 g8 pound for 3minutes. The specimens were then dried at 120 40 40 80 C. for twominutes, and were then heated in an oven 70 lgg 2g 58 at C. for fourminutes. Prior to initial test, the speci- 60 70 s mens were washed inwarm water, dried at 80 C. for 10 g3 3g 88 minutes, ironed, andconditioned at 50% RH. After each 0 100 3 laundering the test pieceswere likewise subjected to iron- 0 90 110 ing and conditioning of 50%RH. 75

Papers having a Kit Number of about 5-6 or below will exhibit only fairoil-repellency; those papers having 8. Kit Number of about 8-10 willhave good oil-repellency, and those having a Kit Number of about 10 andup will have excellent oil-repellency.

Unsized paper hand sheets of 50/50 hardwood/softwood kraft pulp beatento 400 ml. Canadian Standard freeness were impregnated by totalimmersion for 1 minute in about 0.4 percent by weight solution of1,7-bis (per fluorooctanoyl)-4-acrylyl-1,4,7-triazaheptane in acetone.Excess solution was blotted from the hand sheets. The hand sheets werethen dried at 230 F. for approximately one minute and were then testedfor oil resistance by the above-described Kit Test. The Kit Numbers ofthe paper so treated Were 10-11, indicating excellent oil-repellency.

When other fluorocarbon compounds Within the scope of the presentinvention are applied to textiles and paper in the above-describedmanner similar results are obtained, that is to say good oilandwater-repellency is imparted to the textiles and paper so treated.

From the foregoing it is apparent that we have discovered a series ofnovel and valuable compounds which are oiland water-repellent agentswhich also provide maintenance of oleophobic and hydrophobic propertiesof substrate surfaces treated therewith after their repeated exposure tolaundering treatments.

Since various changes and modifications may be made in the inventionwithout departing from the spirit there of, it is intended that allmatter contained in the above description shall be interpreted asillustrative and not in a limiting sense.

We claim:

1. Compounds having the structural formula II I I ll R[CN(C;H:;N)-C;H2x-'NCR1 TR R:- R

wherein (I) R; is a radical selected from the group consisting of (a)perfluoroalkyl having from to 15 carbon atoms, and

(b) a radical having the formula wherein (i) m and n are each integersof from 0 to 0 to 5, with the proviso that the sum of m and n is from 0tell) and provided further that when r is O, m is at least 1,

(ii) X is selected from the group consisting of hydrogen and fluorine,with the proviso that when n is greater than 0, then X is alwayshydrogen,

(iii) p is 0 or 1,

(iv) r is 0 or 1, with the proviso that when the sum of m, n and p isgreater than 0, then r is alw y 0;

(2) x is an integer from 2 to 3,

(3) y is an integer from 1 to 3,

(4) R R and R are independently selected from the group consisting ofhydrogen and alkyl having from 1 to 6 carbon atoms.

2. Compounds according to claim 1 wherein R is a perfluoroalkyl radicalhaving from 6 to 14 carbon atoms.

3. Compounds according to claim 2 wherein R" is selected from the groupconsisting of hydrogen and methyl, and wherein R and R are independentlyselected from the group consisting of hydrogen and alkyl having from 1to 2 carbon atoms.

4. Compounds according to claim 3 wherein R and R are both H.

5. A compound according to claim 4 having the structural formula 6'. Acompound according to claim 4 having the structural formula 7. Acompound according to claim 4 having the structural formula 8. Acompound according to claim 4 having the structural formula 9. Compoundsaccording to claim 1 wherein R, is a radical having the formula whereinm, n, r, p and X have the meanings given in claim 1.

10. Compounds according to claim 9 wherein R is selected from the groupconsisting of hydrogen and methyl and wherein R and R are independentlyselected from the group consisting of hydrogen and alkyl having from 1to 2 carbon atoms.

11, Compounds according to claim 10 wherein R and R are both hydrogen.

12. A compound aCcOrding to claim 11 having the structural formula [(CFCFO(CF CONHC H N COCH=CH 13. A compound according to claim 11 having thestructural formula COCH=CH 22 References Cited UNITED STATES PATENTS2,528,274 10/ 1950 Gunderson 2604O4.5 2,593,737 4/1952 Diesslin et a1260- 514 3,038,820 6/ 1962 Albrecht 260404.5 3,185,539 5/1965 Madison etal. 260 561 3,420,697 1/ 1969 Sweeney et a1. .4 260404.5 3,428,7092/1969 Kleiner 260404.5 3,446,570 5/1969 Sweeney et al. 260404.53,453,333 7/1969 Litt et a1. 260633 3,458,571 7/1969 Tokoli 260404.53,470,256 9/1969 Evans et a1. 260611 FOREIGN PATENTS 1,111,396 4/1968Great Britain 260404.5

LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner US. Cl.X.R.

